CN115842106B - Plate type positive electrode of lead-acid battery and manufacturing process thereof - Google Patents
Plate type positive electrode of lead-acid battery and manufacturing process thereof Download PDFInfo
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- CN115842106B CN115842106B CN202310132471.7A CN202310132471A CN115842106B CN 115842106 B CN115842106 B CN 115842106B CN 202310132471 A CN202310132471 A CN 202310132471A CN 115842106 B CN115842106 B CN 115842106B
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Abstract
The invention discloses a plate type positive electrode of a lead-acid battery and a manufacturing process thereof, and belongs to the technical field of lead-acid batteries. The technical proposal is as follows: the method comprises the following steps: s1, mixing the lead paste, including dry mixing, wet mixing, acid mixing, cooling and adjusting apparent density of the lead paste; s2, sequentially carrying out plate coating, acid spraying, pressing plate and surface drying on the lead plaster obtained in the step S1; s3, curing the lead plaster obtained in the step S2; and S4, drying the lead plaster cured in the step S3. According to the invention, the microstructure of the positive electrode active material is changed by changing the manufacturing process conditions of the positive electrode plate of the lead-acid battery, so that the utilization rate of the positive electrode active material is improved, and the aim of improving the energy density of the lead-acid battery is fulfilled.
Description
Technical Field
The invention relates to the technical field of lead-acid batteries, in particular to a plate-type positive electrode of a lead-acid battery and a manufacturing process thereof.
Background
In order to improve the energy density of the lead-acid battery, engineering technicians tend to reduce the weight of the battery through a mode of thinning the grid, and the mode has the defects that with the thinning of the positive grid, the yield of smelting plates can be reduced on one hand, the waste of energy and manpower is caused, and on the other hand, the lead-acid battery can be failed in advance due to corrosion of the positive grid. Chinese patent No. CN104485454a discloses a lead-acid battery positive electrode lead plaster, which comprises an ionic liquid, wherein the ionic liquid is alkyl imidazole trifluoro methane sulfonate. The alkyl imidazole trifluoro mesylate can improve the hydrogen evolution and oxygen evolution overpotential of the active substance, further inhibit the loss of charge and discharge water and reduce the battery failure caused by water dryness. The alkyl imidazole trifluoro mesylate has lower surface tension and can be well compatible with other substances, so that the inorganic material has higher nucleation rate, therefore, the addition of the alkyl imidazole trifluoro mesylate in the positive lead paste can improve the crystallization rate of lead sulfate in the discharge process, reduce the supersaturation degree and enable the surface of the positive plate to generate loose and porous lead sulfate. However, the patent does not improve the manufacturing process to increase the utilization rate of the positive electrode active material, so as to achieve the purpose of increasing the energy density of the lead-acid battery. Therefore, a new process is needed to increase the energy density of the lead-acid battery without affecting the normal use of the lead-acid battery.
Disclosure of Invention
The invention aims to solve the technical problems that: the defects of the prior art are overcome, and the plate type positive electrode of the lead-acid battery and the manufacturing process thereof are provided, and the manufacturing process conditions of the positive plate of the lead-acid battery are changed, so that the microstructure of the positive electrode active material is changed, the utilization rate of the positive electrode active material is improved, and the aim of improving the energy density of the lead-acid battery is fulfilled.
The technical scheme of the invention is as follows:
in one aspect, the invention provides a manufacturing process of a lead-acid battery plate type positive electrode, which comprises the following steps:
s1 and paste
1) Dry blending: dry blending an active material and a fiber, wherein the active material comprises a barton powder and a red lead powder;
2) Wet mixing: adding deionized water into the mixture obtained after the dry mixing in the step 1) for wet mixing;
3) Acid mixing: adding sulfuric acid aqueous solution into the mixture obtained in the step 2) after wet mixing for acid mixing to obtain lead plaster;
4) And (3) cooling: cooling the lead plaster obtained in the step 3) to 30-40 ℃;
5) Adjusting apparent density of the lead plaster: regulating apparent density of the lead plaster obtained in the step 4) to be 4.45-4.55g/cm by using deionized water 3 ；
S2, sequentially carrying out plate coating, acid spraying, pressing plate and surface drying on the lead plaster obtained in the step 5);
s3, curing the lead plaster obtained in the step S2;
and S4, drying the lead plaster cured in the step S3.
The adding of red lead powder has three functions: firstly, inhibiting oversized tetrabasic lead sulfate particles from being generated in the curing process of the positive plate; secondly, the free lead is promoted to be converted into lead oxide through the strong oxidation of the red lead powder; and thirdly, the red lead powder has better electronic conductivity compared with the barton powder, and can reduce electrochemical polarization in the formation process. When the use amount of the red lead powder is too low, the effect of inhibiting the generation of oversized tetrabasic lead sulfate is not obvious, and the conductivity of the positive plate is poor; when the use amount of the red lead powder is too high, the mechanical strength of the positive plate is reduced.
Preferably, in step S1, the mass ratio of the barton powder, the red lead powder, the fiber, the deionized water and the sulfuric acid aqueous solution in step 2) is (85-95): (5-15): (0.05-0.08): (5-7): (10-12).
Preferably, in the step 1), the oxidation degree of the barton powder is 82-90%, the lead oxide on the outer layer of the barton powder is compact and is difficult to react with sulfuric acid, and the cured positive plate contains higher free lead after the oxidation degree is low, so that the free lead is difficult to be converted into active substances, and the capacity of the positive plate can be reduced; when the oxidation degree is too high, the curing process lacks crosslinking by oxidation of free lead, resulting in poor mechanical strength of the positive electrode plate. The average grain size of the Baton powder is 6-10 mu m, the excessively low grain size corresponds to thinner oxide layer, a large amount of free lead can be oxidized in the paste mixing process, the crosslinking effect formed by the oxidation of the free lead can be reduced in the curing process, and the mechanical strength of the positive plate is poor; the particle size is too high, and corresponds to the oxide layer thicker, and the outer layer of oxide layer reacts with sulfuric acid when the cream and forms the lead sulfate layer, and the lead sulfate layer prevents sulfuric acid from further reacting to the inside of oxide layer, and the inside oxide layer of densification can prevent free lead oxidation in the curing process, leads to positive plate free lead to contain highly, influences positive plate active material quality, and then influences positive plate capacity.
Preferably, in the step 1), the mass percentage of the lead oxide in the red lead powder is 95-99.9%, and when the content of the lead oxide is too low, more free lead is introduced, which is not beneficial to improving the curing quality and forming into active substances. The average grain size of the red lead powder is 1-5 mu m, and when the grain size is too low, the agglomeration can easily occur on the surface with higher specific surface energy, and the dispersion is not facilitated; the higher grain diameter can reduce the specific surface area and reduce the effect of the red lead powder.
Preferably, in step 3), the mass concentration of the aqueous sulfuric acid solution is 52-60%.
The sulfuric acid water solution is used to react with lead oxide to produce lead sulfate, and the lead sulfate reacts with lead oxide continuously to produce a series of basic lead sulfate. When the addition amount of the sulfuric acid aqueous solution is too low, the viscosity of the lead plaster is high, which is not beneficial to coating plates; the addition amount of the sulfuric acid aqueous solution is too high, the apparent density of the lead plaster is reduced, the thickness of the positive plate is not easy to control, the porosity of the positive plate is high, the cycle life is influenced, and the electronic conductivity of the positive plate is influenced. In addition, the mass concentration of the sulfuric acid aqueous solution is 52-60%, and the barton powder oxide layer has relatively inert chemical property, so that the sulfuric acid aqueous solution is unfavorable for reacting with the oxide layer when the concentration is too low, and is strong in reaction with lead oxide when the concentration is too high, and the local ultra-high temperature can cause insufficient activity of lead sulfate, so that basic lead sulfate is unfavorable to be generated.
The fiber can strengthen the mechanical strength of the positive plate, and the addition amount of the fiber accounts for 0.05-0.08% of the total amount of the active materials. When the fiber addition amount is too low, the effect of strengthening the mechanical strength of the positive plate is poor; too high an amount of addition affects the electron conductivity of the positive electrode plate. Before adding the fiber, the fiber is firstly dried at 50-80 ℃ for 3-6 hours, and the drying function is to remove the water in the fiber, so that the fiber has better dispersibility.
The deionized water added in the invention is divided into two parts, one part is directly used for mixing paste, and the other part is called formula water. The formula water is mainly used for wetting the active substances, so that the active substances react with the sulfuric acid aqueous solution more uniformly. The dosage of the formula water accounts for 5-7% of the total amount of the active substances, the active substances cannot be fully wetted when the dosage is too low, the viscosity of the active substances is high when the dosage is too high, the active substances are easy to adhere to the inner wall of a paste mixing machine, and the stirring is uneven. Another part is provided withDeionized water is used to adjust the apparent density of the lead plaster, and this part of deionized water is called adjusting water. Adjusting apparent density of the lead plaster to 4.45-4.55g/cm by adjusting water 3 If the apparent density is too low, the porosity of the positive plate after solidification is too high, which is not beneficial to the cycle life and affects the electronic conductivity of the positive plate; if the apparent density is too high, the porosity of the positive plate is too low, which is unfavorable for charge and discharge performance.
Preferably, in the step S1, the dry mixing time is 6-10min; the wet mixing time is 5-8min; the acid adding time is 6-12min in the acid mixing process, and the stirring time after acid adding is 14-18min.
The dry mixing is to fully and uniformly mix the barton powder, the red lead powder and the fibers, the mixing is not uniform due to the too short dry mixing time, the effect of inhibiting the generation of ultra-large tetrabasic lead sulfate by the red lead powder is reduced, and the consistency of the produced positive plate is poor; too long dry mixing time can affect production efficiency.
After the dry mixing is completed, the paste mixing machine continues stirring and rapidly adds the formula water into the wet mixing stage. The wet mixing time is 5-8min, if the time is too short, the active substances are not uniformly wetted, and if the time is too long, part of water can volatilize.
After the wet mixing is finished, the mixture is continuously stirred with a paste machine, and sulfuric acid aqueous solution is added to enter an acid mixing stage. The principle of the acid mixing stage is that the reaction heat generated when sulfuric acid reacts with active substances is utilized to raise the temperature of the lead plaster, and tetrabasic lead sulfate seed crystals are generated in the lead plaster. The acid adding time is controlled to be 6-12min, and lead sulfate which is not active can be locally generated when the acid is added too fast, and larger tetrabasic lead sulfate crystal grains can be easily generated; too slow acid addition can result in insufficient temperature of the lead plaster, affecting the formation of tetrabasic lead sulphate seed crystals. And after the acid addition is finished, stirring is continued for 14-18min, the total acid mixing time is 20-30min, the tetrabasic lead sulfate seed crystal is unevenly mixed if the acid mixing time is too short, the tetrabasic lead sulfate seed crystal can grow into larger crystal grains if the acid mixing time is too long, and the oversized tetrabasic lead sulfate crystal grains continue to grow after solidification, so that the formation and the capacity of a positive plate are affected.
And after the acid mixing is finished, cooling by using a cooling device of a paste mixing machine, and rapidly cooling the lead paste to 30-40 ℃ for the purpose of preventing the tetrabasic lead sulfate seed crystal from continuously growing. Cooling downAfter the completion, the apparent density was adjusted to 4.45-4.55g/cm by conventional operation 3 。
And (3) after the paste mixing is finished, entering a coating process according to conventional operation, and after the coating process is finished, entering an acid spraying process, wherein the mass concentration of sulfuric acid aqueous solution for acid spraying is 30-32%. Because the oxidation layer of the Baton powder has stronger chemical inertia, when the concentration of the sulfuric acid aqueous solution is too low, a complete lead sulfate layer is not easy to form on the surface of the positive plate, and the viscosity of lead paste is higher, so that the subsequent pressing plate is not facilitated; when the concentration of the sulfuric acid aqueous solution is too high, the surface of the positive plate is thicker in the sulfuric acid layer, which is unfavorable for formation of the positive plate. After the acid spraying process is finished, the polar plate is subjected to acid spraying and then is driven by equipment to pass through two rubber rollers with 15kg of weight and wrapped with pure cotton material coarse cloth outside, and the polar plate is rolled by the gravity of the rubber rollers; then the anode plate is conveyed into a surface drying kiln, the anode plate is subjected to surface drying in the drying kiln, and finally the anode plate is subjected to a curing and drying stage.
Preferably, in step S3, the curing comprises two stages, wherein the curing temperature in the first stage is 50-55 ℃, the relative humidity is 80-90%, and the curing time is 30-36h. The main function of the stage is to oxidize the surface of the grid, the surface of the oxidized grid is rough, and the generated oxide can react with the lead plaster, so that the lead plaster has better binding force with the grid. The second stage has curing temperature of 65-70 deg.c, relative humidity of 90-98% and curing time of 36-48 hr. The primary function of this stage is to grow the tetrabasic lead sulfate seed crystals, and because the tetrabasic lead sulfate crystals are interlaced with each other to form a space skeleton structure (as shown in the SEM image of example 1 in fig. 1), so that more pores are generated in the positive plate, and after formation, the active material inherits the tetrabasic lead sulfate space skeleton structure (as shown in the SEM image of example 1 in fig. 3), so that the electrolyte is convenient to permeate, the charging and discharging are facilitated, and the active material is fully exerted, thus the positive plate has high capacity (as shown in fig. 5). In addition, as the tetrabasic lead sulfate crystal is relatively large, the external sulfuric acid amount of the crystal is sufficient in the formation and charging processes, beta-type lead dioxide is generated, and the capacity of the positive plate is ensured; the internal sulfuric acid of the crystal is deficient, and alpha-type lead dioxide is generated, so that the cycle life of the positive plate is ensured.
Preferably, in step S4, the drying includes three stages, and the drying in the three stages adopts air drying; the drying temperature in the first stage is 75-80deg.C, relative humidity is 65-70%, and drying time is 12-16 hr. This stage, compared to the second stage of curing, increases the temperature and reduces the relative humidity, mainly by evaporating most of the free water in the positive plate. And the relative humidity should not be reduced too low, otherwise the positive plate is liable to crack. The second stage has a drying temperature of 80-85deg.C, a relative humidity of 40-50%, and a drying time of 10-12 hr. The effect of this stage is to further reduce the moisture in the positive plate. The drying temperature in the third stage is 70-75deg.C, and the drying time is 8-10h. The temperature at this stage is too high or the time is too long, so that the content of free water in the positive plate is too low, the brittleness of the positive plate is large, and the phenomenon of surface cracking or grid paste separation of the positive plate easily occurs in the process of transferring or assembling the battery, thereby influencing the cycle life of the battery. And after curing and drying, transferring to a subsequent process.
On the other hand, the invention also provides the lead-acid battery plate type positive electrode prepared by the manufacturing process.
Compared with the prior art, the invention has the following beneficial effects:
the invention ensures that the main component in the positive plate is tetrabasic lead sulfate by controlling the proportion of each component in the lead plaster, the plaster mixing process, the physical state of the lead plaster, the acid spraying process, the curing and drying process. The tetrabasic lead sulfate is mutually crosslinked to form a space network structure, so that larger pores and higher porosity are generated in the polar plate, and the pores in the polar plate still exist after formation, which provides favorable conditions for the diffusion depth and diffusion speed of electrolyte in the discharging process of the battery, improves the utilization rate of active substances in the deep part of the polar plate, slows down concentration polarization caused by rapid consumption of sulfuric acid in the electrolyte on the surface of the active substances, and finally shows higher discharge capacity under the condition of the same active substances compared with the plate-type positive plate manufactured by the traditional process, thereby improving the energy density of the battery.
Drawings
Fig. 1 is an SEM image of the internal microstructure of the positive plate of example 1, at a magnification of 2000 x, with a scale length of 10 μm.
Fig. 2 is an SEM image of the internal microstructure of the positive plate of comparative example 1, magnified 2000 times, marked with a length of 50 μm.
Fig. 3 is an SEM image of the internal microstructure of the positive electrode plate of example 1 after completion of formation, the SEM image being at 2000 x magnification, the scale length being 10 μm.
Fig. 4 is an SEM image of the internal microstructure of the positive electrode plate of comparative example 1 after completion of formation, the magnification of the SEM image being 2000 x, the scale length being 50 μm.
Fig. 5 is a discharge capacity test chart of the assembled battery of example 1 and comparative example 1.
Detailed Description
The invention is further illustrated below with reference to examples.
The battery assembly methods in the following examples and comparative examples were: GFM200E batteries were assembled by matching the GFME type positive plates, applied at 505 g/piece, with the shop conventional GFME type negative plates, according to the procedure described in the examples and comparative examples.
Comparative example 1
GFM200E batteries were assembled using the same weight shop GFME type conventional positive and negative plates. The nominal capacity of the battery is 200Ah, the discharge multiplying power is 10hr, and the discharge cut-off voltage is 1.8V.
Example 1
The manufacturing process of the lead-acid battery plate type positive electrode of the embodiment comprises the following steps:
s1 and paste
1) Dry blending: weighing the barton powder and the red lead powder in a paste mixing machine, and continuously adding the dried fibers to dry-mix for 6min; wherein the Baton powder amount accounts for 85% of the total amount of the active substances, the oxidation degree is 82%, and the average particle size is 6 mu m; the consumption of the red lead powder is 15% of the total amount of the active substances, the content of the lead tetraoxide in the red lead powder is 95%, and the average grain diameter is 1 mu m; before the fiber is used, the fiber is firstly dried, the drying temperature is 50 ℃, the drying time is 6 hours, and the fiber dosage is 0.05% of the total amount of active substances;
2) Wet mixing: adding deionized water accounting for 5% of the total amount of the active substances into the mixture obtained after the dry mixing in the step 1) for wet mixing, wherein the wet mixing time is 8min;
3) Acid mixing: adding 10% of sulfuric acid aqueous solution of the total amount of active substances into the wet-mixed mixture in the step 2) for acid mixing to obtain lead plaster; wherein the mass concentration of the sulfuric acid aqueous solution is 52%, the acid adding time is 6min, and stirring is continued for 18min after the acid adding is finished;
4) And (3) cooling: cooling the lead plaster obtained in the step 3) to 30 ℃;
5) Adjusting apparent density of the lead plaster: regulating apparent density of the lead plaster obtained in the step 4) to be 4.45 g/cm by using deionized water 3 ；
S2, sequentially carrying out plate coating, acid spraying, pressing plate and surface drying on the lead plaster obtained in the step 5), wherein the mass concentration of the sulfuric acid aqueous solution for acid spraying is 30%;
s3, curing the lead plaster obtained in the step S2, wherein the temperature of the first curing stage is 50 ℃, the relative humidity is 80%, and the time is 30 hours; the temperature of the second curing stage is 65 ℃, the relative humidity is 90%, and the time is 36h;
s4, drying the lead plaster cured in the step S3, wherein the temperature of the first drying stage is 75 ℃, the relative humidity is 65%, and the time is 12 hours; the temperature in the second stage of drying is 80 ℃, the relative humidity is 40%, and the time is 10 hours; the third drying stage is simple air blast drying, the temperature is 70 ℃, and the drying time is 8 hours.
The materials, the shape selection or the operation and the like which are not mentioned in the process are carried out conventionally.
As shown in the SEM diagram of the positive plate prepared in this example, as shown in FIG. 1, after the positive plate of this example is cured and dried, tetrabasic lead sulfate particles are crosslinked with each other to form a three-dimensional network structure with larger pores, while as shown in FIG. 2, the lead paste particles on the positive plate of comparative example 1 are fine and have no obvious pores.
Fig. 3 to 4 are microstructure diagrams of the positive electrode plates of fig. 1 to 2 after being formed, and as can be seen from fig. 3, the positive electrode plates of the present embodiment form developed, uniform and larger "ant-hole" shaped pores in the positive electrode plates after being formed, and the pores are mutually communicated. The structure is favorable for the diffusion depth and diffusion speed of electrolyte, lead sulfate generated in the discharging process is not easy to block larger pores, the voltage drop of the battery terminal caused by concentration polarization is slowed down, and the utilization rate of active substances is improved. As can be seen from the microscopic morphology of the conventional positive electrode plate formed in comparative example 1 corresponding to fig. 4, the pores in the positive electrode plate in comparative example 1 are smaller and unevenly distributed, so that the pores are easily blocked by lead sulfate generated in the discharge process, the diffusion depth and diffusion speed of the electrolyte in the positive electrode plate are seriously reduced after the pores are blocked by lead sulfate, and finally the battery reaches the discharge termination voltage earlier due to concentration polarization, and the utilization rate of active substances is lower.
The positive electrode plate prepared in this example was assembled into a battery, and was discharged for 10hr after acid cycle formation, as shown in fig. 5, and the battery capacity was finally measured to be 1.15 times that of comparative example 1.
Example 2
The manufacturing process of the lead-acid battery plate type positive electrode of the embodiment comprises the following steps:
s1 and paste
1) Dry blending: weighing the barton powder and the red lead powder in a paste mixing machine, and continuously adding the dried fibers to dry-mix for 10min; wherein the Baton powder amount accounts for 95% of the total amount of the active substances, the oxidation degree is 90%, and the average particle size is 10 mu m; the consumption of the red lead powder is 5% of the total amount of the active substances, the content of the lead tetraoxide in the red lead powder is 99.9%, and the average grain diameter is 5 mu m; before the fiber is used, the fiber is firstly dried, the drying temperature is 80 ℃, the drying time is 3 hours, and the fiber dosage is 0.08% of the total amount of active substances;
2) Wet mixing: adding deionized water accounting for 7% of the total amount of the active substances into the mixture obtained after the dry mixing in the step 1) for wet mixing, wherein the wet mixing time is 5min;
3) Acid mixing: adding a sulfuric acid aqueous solution with the total amount of 12% of the active substances into the wet-mixed mixture in the step 2) for acid mixing to obtain lead plaster; wherein the mass concentration of the sulfuric acid aqueous solution is 60%, the acid adding time is 12min, and stirring is continued for 14min after the acid adding is finished;
4) And (3) cooling: cooling the lead plaster obtained in the step 3) to 40 ℃;
5) Adjusting apparent density of the lead plaster: regulating apparent density of the lead plaster obtained in the step 4) to be 4.55g/cm by using deionized water 3 ；
S2, sequentially carrying out plate coating, acid spraying, pressing plate and surface drying on the lead plaster obtained in the step 5), wherein the mass concentration of the sulfuric acid aqueous solution for acid spraying is 32%;
s3, curing the lead plaster obtained in the step S2, wherein the temperature of the first stage of curing is 55 ℃, the relative humidity is 90%, and the time is 36 hours; the temperature of the second curing stage is 70 ℃, the relative humidity is 98%, and the time is 48 hours;
s4, drying the lead plaster cured in the step S3, wherein the temperature of the first drying stage is 80 ℃, the relative humidity is 70%, and the time is 16 hours; the temperature in the second stage of drying is 85 ℃, the relative humidity is 50%, and the time is 12 hours; the third drying stage is simple air blast drying, the temperature is 75 ℃, and the drying time is 10 hours.
The materials, the shape selection or the operation and the like which are not mentioned in the process are carried out conventionally.
The positive electrode plate prepared in this example was assembled into a battery, and was discharged for 10hr after acid cycle formation, and the battery capacity was finally measured to be 1.18 times that of comparative example 1.
Example 3
The manufacturing process of the lead-acid battery plate type positive electrode of the embodiment comprises the following steps:
s1 and paste
1) Dry blending: weighing the barton powder and the red lead powder in a paste mixing machine, and continuously adding the dried fibers to dry-mix for 8min; wherein the Baton powder amount accounts for 90% of the total amount of the active substances, the oxidation degree is 87%, and the average particle size is 8 mu m; the consumption of the red lead powder is 10% of the total amount of the active substances, the content of the lead tetraoxide in the red lead powder is 97%, and the average grain diameter is 3 mu m; the fiber is firstly dried before use, the drying temperature is 65 ℃, the drying time is 4.5 hours, and the fiber dosage is 0.065% of the total amount of active substances;
2) Wet mixing: adding deionized water accounting for 6% of the total amount of the active substances into the mixture obtained after the dry mixing in the step 1) for wet mixing, wherein the wet mixing time is 6min;
3) Acid mixing: adding 11% of sulfuric acid aqueous solution of the total amount of active substances into the wet-mixed mixture in the step 2) for acid mixing to obtain lead plaster; wherein the mass concentration of the sulfuric acid aqueous solution is 55%, the acid adding time is 8min, and stirring is continued for 16min after the acid adding is finished;
4) And (3) cooling: cooling the lead plaster obtained in the step 3) to 35 ℃;
5) Adjusting apparent density of the lead plaster: regulating apparent density of the lead plaster obtained in the step 4) to be 4.5 g/cm by using deionized water 3 ；
S2, sequentially carrying out plate coating, acid spraying, pressing plate and surface drying on the lead plaster obtained in the step 5), wherein the mass concentration of the sulfuric acid aqueous solution for acid spraying is 31%;
s3, curing the lead plaster obtained in the step S2, wherein the temperature of the first curing stage is 52 ℃, the relative humidity is 85%, and the time is 32 hours; the temperature of the second curing stage is 68 ℃, the relative humidity is 94%, and the time is 42h;
s4, drying the lead plaster cured in the step S3, wherein the temperature of the first stage of drying is 78 ℃, the relative humidity is 67%, and the time is 14 hours; the temperature in the second stage of drying is 83 ℃, the relative humidity is 45%, and the time is 11h; the third drying stage is simple air blast drying, the temperature is 72 ℃, and the drying time is 9h.
The materials, the shape selection or the operation and the like which are not mentioned in the process are carried out conventionally.
The positive electrode plate prepared in this example was assembled into a battery, and was discharged for 10hr after acid cycle formation, and the battery capacity was finally measured to be 1.16 times that of comparative example 1.
Comparative example 2
The difference from example 1 is that: the red lead powder is replaced by the barton powder.
The battery capacity assembled in comparative example 2 was measured to be 0.9 times that of example 1, and the battery capacity was reduced, mainly because comparative example 2 lacks the red lead powder to inhibit the growth of tetrabasic lead sulfate, and ultra-large-sized tetrabasic lead sulfate is generated in the positive electrode plate, which is difficult to be formed, resulting in lower battery capacity.
Comparative example 3
The difference from example 1 is that: and replacing the barton powder with red lead powder.
The assembled battery of comparative example 3 was measured to have a capacity 0.95 times that of example 1, and the battery was reduced because the barton powder was the main raw material for generating tetrabasic lead sulfate, and in the absence of the barton powder, a developed space network structure pore could not be formed inside the positive electrode plate by generating tetrabasic lead sulfate, and the electrolyte transmission resistance was large at the time of discharge.
Comparative example 4
The difference from example 1 is that: the content of the Baton powder is 10% of the total amount of the active substances, and the content of the red lead powder is 90% of the total amount of the active substances.
The battery capacity assembled in comparative example 4 was measured to be 0.976 times that of the battery of example 1, and the battery capacity was reduced because the barton powder is the main raw material for generating tetrabasic lead sulfate, and under the condition of low barton powder content, the generated tetrabasic lead sulfate forms underdeveloped space network structure pores inside the polar plate, and the electrolyte transmission resistance is large during discharge.
Comparative example 5
The difference from example 1 is that: in the step 5), the apparent density of the lead plaster is regulated to be 4.6g/cm 3 。
The battery capacity assembled in comparative example 5 was measured to be 0.992 times that of example 1, and the battery capacity was reduced because an excessively high apparent density increased the bulk density of tetrabasic lead sulfate in the electrode plate, resulting in a lower pore diameter and porosity of the positive electrode plate, and reduced electrolyte diffusion depth and diffusion rate, as compared to example 1, and thus reduced battery capacity.
Comparative example 6
The difference from example 1 is that: in the step 5), the apparent density of the lead plaster is regulated to be 4.4g/cm 3 。
The battery capacity assembled in comparative example 6 was measured to be 0.996 times that of example 1, and the battery capacity was reduced because too low a view density resulted in an increase in pore diameter and porosity due to crosslinking between tetrabasic lead sulfate inside the electrode plate, and although the electrolyte diffusion depth and diffusion speed were increased, an electron transport path was increased, resulting in an increase in ohmic polarization degree inside the positive electrode plate, and thus the battery capacity was reduced as compared with example 1.
Comparative example 7
The difference from example 1 is that: in the step S3, the temperature of the first stage of curing is 65 ℃, the relative humidity is 90%, and the time is 36h; the second stage of curing was at 50℃and 80% relative humidity for 30 hours.
The assembled battery capacity of comparative example 7 was measured to be 0.985 times the battery capacity of example 1. The battery capacity decreases because: the temperature, humidity and time of the first stage of curing are higher than or longer than those of the second stage, the tetrabasic lead sulfate seed crystal in the positive plate can grow rapidly, the effect of an oxide layer formed at the interface of the grid and the lead plaster is reduced, the combination between the grid and the lead plaster is poor, the resistance of the plate is increased, and finally the internal resistance of the battery is high. Thus, the battery capacity was reduced as compared with example 1.
Comparative example 8
The difference from example 1 is that: in step S4, the relative humidity in the first stage of drying is 30%.
The battery capacity assembled in comparative example 8 is 0.988 times of the battery capacity assembled in example 1, and the battery capacity is reduced because the humidity is set to be too low in the first stage of drying, which can cause the rapid evaporation of water in the positive plate, the tensile stress generated in the drying process can not be released in time, the surface of the positive plate is caused to generate stress cracks, the continuity of active substances is influenced, the current is unevenly distributed on the positive plate, and part of active substances cannot exert capacity; on the other hand, the tensile stress damages the bond of the lead plaster and the grid, resulting in an increase in the internal resistance of the battery, and thus the battery capacity is reduced as compared with example 1.
Claims (5)
1. The manufacturing process of the lead-acid battery plate type positive electrode is characterized by comprising the following steps of:
s1 and paste
1) Dry blending: dry blending an active material and a fiber, wherein the active material comprises a barton powder and a red lead powder;
2) Wet mixing: adding deionized water into the mixture obtained after the dry mixing in the step 1) for wet mixing;
3) Acid mixing: adding sulfuric acid aqueous solution into the mixture obtained in the step 2) after wet mixing for acid mixing to obtain lead plaster;
4) And (3) cooling: cooling the lead plaster obtained in the step 3) to 30-40 ℃;
5) Adjusting apparent density of the lead plaster: regulating apparent density of the lead plaster obtained in the step 4) to be 4.45-4.55g/cm by using deionized water 3 ；
S2, sequentially carrying out plate coating, acid spraying, pressing plate and surface drying on the lead plaster obtained in the step 5), wherein the pressing plate means that the polar plate is driven by equipment to pass through two rubber rollers after acid spraying, and the polar plate is rolled by the self gravity of the rubber rollers;
s3, curing the lead plaster obtained in the step S2;
s4, drying the lead plaster cured in the step S3;
in the step S3, the curing comprises two stages, wherein the curing temperature in the first stage is 50-55 ℃, the relative humidity is 80-90%, and the curing time is 30-36h; the curing temperature in the second stage is 65-70 ℃, the relative humidity is 90-98%, and the curing time is 36-48h;
in the step S4, the drying comprises three stages, wherein the drying temperature in the first stage is 75-80 ℃, the relative humidity is 65-70%, and the drying time is 12-16h; the second stage has a drying temperature of 80-85deg.C, a relative humidity of 40-50%, and a drying time of 10-12 hr; the drying temperature in the third stage is 70-75deg.C, and the drying time is 8-10h;
in the step S1, the mass ratio of the Baton powder, the red lead powder, the fiber to the deionized water and the sulfuric acid aqueous solution in the step 2) is (85-95): (5-15): (0.05-0.08): (5-7): (10-12);
in the step S1, the dry mixing time is 6-10min; the wet mixing time is 5-8min; the acid adding time is 6-12min in the acid mixing process, and the stirring time after acid adding is 14-18min.
2. The process for manufacturing a plate-type positive electrode for a lead-acid battery according to claim 1, wherein in the step 1), the oxidation degree of the barton powder is 82-90%, and the average particle size is 6-10 [ mu ] m.
3. The manufacturing process of the lead-acid battery plate type positive electrode according to claim 1, wherein in the step 1), the mass percentage of the lead tetraoxide in the red lead powder is 95-99.9%, and the average grain size is 1-5 mu m.
4. The process for manufacturing a plate-type positive electrode for a lead-acid battery according to claim 1, wherein in the step 3), the mass concentration of the aqueous sulfuric acid solution is 52-60%.
5. A lead acid battery plate positive electrode prepared by the manufacturing process of any one of claims 1-4.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103606653A (en) * | 2013-10-21 | 2014-02-26 | 安徽省华森电源有限公司 | Automatic curing energy-saving technology of secondary lead regenerated accumulator plate |
| CN107623108A (en) * | 2017-09-26 | 2018-01-23 | 安徽轰达电源有限公司 | A kind of solidifying lead acid battery polar plate drying process |
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| CN104221189B (en) * | 2012-02-14 | 2017-02-22 | 新神户电机株式会社 | Positive electrode plate for lead acid battery, method for producing said electrode plate, and lead acid battery using said positive electrode plate |
| CN104485454A (en) * | 2014-12-10 | 2015-04-01 | 天能电池集团有限公司 | Positive electrode lead plaster of lead acid storage battery |
| CN106384821A (en) * | 2016-11-14 | 2017-02-08 | 超威电源有限公司 | Lead acid storage battery positive electrode lead paste |
| CN108306058B (en) * | 2017-01-12 | 2020-09-29 | 广州赋力实业有限公司 | Preparation method of lead-acid storage battery |
| CN107146890B (en) * | 2017-03-24 | 2019-10-29 | 淄博火炬能源有限责任公司 | High temperature modification valve-regulated lead-acid battery and preparation method thereof |
| CN108630902B (en) * | 2018-03-28 | 2021-06-29 | 天能电池集团股份有限公司 | Manufacturing process of lead storage battery pole plate |
| CN109873124A (en) * | 2019-01-31 | 2019-06-11 | 安徽超威电源有限公司 | A kind of power lead-acid storage battery high temperature curing process |
| CN111129612B (en) * | 2019-12-12 | 2022-07-26 | 双登集团股份有限公司 | Method for prolonging cycle service life of positive electrode of lead-carbon battery |
| CN113675397B (en) * | 2021-08-23 | 2023-04-11 | 浙江巨江电源制造有限公司 | Deep-cycle long-life lead-acid storage battery lead paste for parking, battery thereof and manufacturing process method of battery |
| CN114204033A (en) * | 2021-12-28 | 2022-03-18 | 河南超威正效电源有限公司 | Lead paste of lead-acid storage battery, preparation method of lead paste, pole plate and high-temperature curing process of pole plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103606653A (en) * | 2013-10-21 | 2014-02-26 | 安徽省华森电源有限公司 | Automatic curing energy-saving technology of secondary lead regenerated accumulator plate |
| CN107623108A (en) * | 2017-09-26 | 2018-01-23 | 安徽轰达电源有限公司 | A kind of solidifying lead acid battery polar plate drying process |
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